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EP2426724A1 - Procédé de production de cellules photovoltaïques - Google Patents

Procédé de production de cellules photovoltaïques Download PDF

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Publication number
EP2426724A1
EP2426724A1 EP10175311A EP10175311A EP2426724A1 EP 2426724 A1 EP2426724 A1 EP 2426724A1 EP 10175311 A EP10175311 A EP 10175311A EP 10175311 A EP10175311 A EP 10175311A EP 2426724 A1 EP2426724 A1 EP 2426724A1
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EP
European Patent Office
Prior art keywords
insulating layer
semiconductor
process according
implantation
implanted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10175311A
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German (de)
English (en)
Inventor
Mourad Yedji
Guy Terwagne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Facultes Universitaires Notre Dame de la Paix
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Facultes Universitaires Notre Dame de la Paix
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Facultes Universitaires Notre Dame de la Paix filed Critical Facultes Universitaires Notre Dame de la Paix
Priority to EP10175311A priority Critical patent/EP2426724A1/fr
Priority to CN2011800426403A priority patent/CN103081131A/zh
Priority to US13/820,232 priority patent/US20130273684A1/en
Priority to EP11752224.3A priority patent/EP2612368A1/fr
Priority to PH1/2013/500338A priority patent/PH12013500338A1/en
Priority to PCT/EP2011/065255 priority patent/WO2012028738A1/fr
Priority to JP2013526498A priority patent/JP2013536993A/ja
Publication of EP2426724A1 publication Critical patent/EP2426724A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/128—Annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/162—Non-monocrystalline materials, e.g. semiconductor particles embedded in insulating materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention is related to a process for producing photovoltaic cells.
  • Si-QDs silicon quantum dots
  • VLS vapor-liquid-solid process
  • HWCVD hot-wire chemical vapor deposition
  • Silicon nanocrystals in the form of a powder were developed and incorporated in liquid silica by chemical way and subsequently used in photovoltaic cells as described in " Silicon nanocrystals as light converter for solar cells", Thin Solid Films, 451-452 (2004) 384 by V. Svrcek et Al.
  • Ion implantation is a known process for doping surface layers of semiconductors to produce p-n junction.
  • the fluence, the implantation energy and the subsequent thermal treatment are adjusted to obtain very small doping concentration.
  • the fluence is then typically less than 10 16 at./cm 2 to avoid precipitation of the dopant and maintain acceptable carrier mobility and lifetime.
  • the present invention aims to provide a process for the production of photovoltaic cells that does not present the drawbacks of prior art.
  • the present invention also aims to provide photovoltaic cells produced by the process.
  • the present invention is related to a process for the manufacturing of process for the manufacturing of a photovoltaic cell comprising the steps of:
  • the process of the invention comprises one or a suitable combination of the following features:
  • Fig. 1 Represents schematically of an example of process according to the invention with front and back conducting contacts.
  • Fig. 3 Represents the effect of the annealing time on Si depth profiles extracted from RBS measurements of sample implanted with a Si multiple energy implantations of 20, 35, 80 keV to fluences of 2.1 x 10 16 , 4.2 x 10 16 and 1.4 x 10 17 Si + /cm 2 .
  • Si depth profile becomes more uniform after 1 hour annealing time.
  • Fig. 4 illustrates the effect of the annealing time at 1100 °C on the PL-spectra for different implanted fluences: (a) 6 x 10 16 Si/cm 2 , (b) 1 x 10 17 Si/cm 2 , (c) 1.4 x 10 17 Si/cm 2 , (d) 2 x 10 17 Si/cm 2 . All samples were passivated.
  • Fig. 5 illustrates the effect of implanted fluence on the PL-spectra recorded in unpassivated samples for a fixed annealing time at 60 min.
  • Fig. 6 represents TEM images of Si QDs in 240 nm SiO 2 .
  • Fig. 7 represents an example of a photovoltaic cell produced according to the invention, having a continuous layer transparent front contact (TCO: transparent conducting oxide, such as Indium Tin Oxide or the like).
  • TCO transparent conducting oxide, such as Indium Tin Oxide or the like.
  • Fig. 8 represents an example of a photovoltaic cell produced according to the method of the invention, having both conducting contacts located on the rear side, with vias.
  • Fig. 9 represents a cross section of an example of a photovoltaic cell produced according to the invention with back contacts only and without vias.
  • Fig. 10 represents a 3D view of a photovoltaic cell according to the invention showing interdigitated back contacts.
  • the present invention is related to a process for producing photovoltaic cells using quantum dots in their active areas. Such kind of QDs permits to improve the average efficiency of photovoltaic devices. More particularly, the present invention aims to provide a simplified process for producing photovoltaic cells oxide layers containing semiconductors QDs while maintaining a good control of QDs size, distribution and density.
  • the present invention also provides QDs production without contaminating the substrate with potential impurities and thus reduces oxide layer contamination.
  • the diffusion of the doping agent toward the substrate is also avoided.
  • the first step of the process of the invention is to provide a semiconductor substrate comprising an insulating layer on its top surface.
  • the semiconductor is preferably selected from the group consisting of silicon and germanium.
  • the insulating layer is obtained by chemically treating the surface of the semiconductor with oxidizing, carburizing or nitridizing species.
  • oxidizing, carburizing or nitridizing species In case of a silicon substrate, this produces silicon dioxide, silicon carbide or silicon nitride insulating layer.
  • said insulating layer can be obtained by chemical vapour deposition, or any alternative deposition method known in the art.
  • semiconductor ions are implanted in the insulating layer, resulting in an excess of the atomic concentration of the semiconductor in comparison with the stoechiometric composition of the insulating layer.
  • the maximum excess concentration of said semiconductor is comprised between 20 and 36%, preferably about 28%.
  • the implanted semiconductor ion is preferably selected from the group consisting of silicon and germanium.
  • the energy profile of the ions during the implantation comprises several energies, leading to a rectangular implantation profile (plateau profile).
  • plateau profile This is usually obtained by using several quasi monoenergetic ion beams (Gaussian profile). For that reason such kind of plateau profile are usually called "multiple implantations".
  • the main advantage of such multiple implantations is to obtain Si-QDS distributed from the extreme surface of the insulating layer to the insulating layer/semiconductor interface thereby improving cells efficiency.
  • Plateau energy profile can be obtained by any other method known in the art.
  • the obtained implanted insulator is then thermally treated at a sufficient temperature sufficient to induce nucleation and growth of the semiconductor atoms in excess to stoechiometric composition, thereby producing QDs.
  • the thermal treatment temperature is selected in order to control QDs density (number of nucleus) and size: larger temperature induces lower number of nucleus and increases growth of the nucleus, giving rise to lower number of larger QDs.
  • the thermal treatment is performed at a temperature above 1000°C, more preferably about 1100°C.
  • the thermal treatment is preferably performed in an inert atmosphere such as nitrogen.
  • the QDs can then be doped by any suitable dopant by an additional implantation step.
  • the dopant can be either of p-type in case of n-type substrate or n-type in case of p-type substrate, generating a p-n or n-p junction for collecting the charge carrier generated by incoming light.
  • p-type dopant is boron.
  • n-type dopant is Phosphorous.
  • a second thermal treatment can advantageously be performed after implantation of the dopant to obtain the final junction structure, with dopant at substitution sites, and relaxing defects induced by the implantation process.
  • Front and back contacts may then be deposited on front and back surface of the substrate.
  • Front contact can be either opaque electrode covering partially the produced photovoltaic cell as represented in Fig. 1 , or transparent conducting electrodes, such as those produced by ITO material as represented in Fig. 7 .
  • Back contact can be opaque electrode, preferably aluminium.
  • all contacts may be located on the back side of the cell as represented in Fig. 8 .
  • This kind of design advantageously reduces the shadowing of the cell by the contacts, thereby improving the conversion efficiency of the photovoltaic cell.
  • the current arising from the front layer may be collected in this case by any known methods, for example through vias, such as described in patent application US 2004/261839 or according to the so called emitter wrap-through technology, such as described in in document WO 2009/077103 .
  • back conducting contacts are deposited on alternating P+ doped area and N+ doped area, without vias, as represented in Fig. 9 .
  • excitons produced in the QD's diffuses through the substrate and the charge carriers are then separated and collected by the electrical fields induced by the PN junctions on the back side.
  • Said conducting contacts on the rear side may advantageously form at least two interdigitated grid electrodes as represented in fig. 10 .
  • the photovoltaic cell of the present invention can be included in a larger stack of cells, the back contact of the photovoltaic cell of the invention being the top electrode of the subsequent cell in the stack.
  • All SiO 2 /Si samples were produced by thermal oxidation, at high temperature ( ⁇ 1100°C under oxygen flow), of a Si (100) wafer.
  • the gas flow was about ⁇ 1 L/min.
  • the thickness and stoichiometry of all oxides were determined by both (RBS) and ellipsometry techniques. Both techniques prove the high quality of the oxide in terms of stoichiometry and purity.
  • the results obtained by ellipsometry show that the variation of refractive index of the oxide layers is very close to the theoritical SiO 2 curves. From this it can be concluded that these layers are perfectly stoichiometric.
  • a series of thin oxide layers were thermally synthesised and characterized with the above conditions and their thickness were between 100 and 300 nm.
  • One of the main problems was that during the oxidation, the oxide was grown onto both top and bottom surfaces of the wafer.
  • development process was used, namely, coating surface A (top) with a photoresist, then submerging the sample in a HF (5%) bath to remove the oxide from the back surface and finally the use of an organic solvent to remove the polymer from the surface A.
  • the wafers were then annealed at 1100°C under nitrogen flow for 15, 30, and 60 min. Special care was taken to avoid oxidation of the samples inside the furnace.
  • SiO 2 implanted coupons of 1 x 1 cm 2 were specially cut for cell fabrication, they were doped by 26 keV B + ions with a fluence of 1.5 x 10 15 B + /cm 2 and heated at 800°C.
  • a comb electrode on top side was deposited by evaporation through a mask whereas back contact was achieved by the deposition of an Al layer.
  • the thickness of the Al contacts was 800 nm.
  • One of the advantages of ion implantation is that Boron implantation (for doping) is performed after annealing (QD's precipitation annealing), thus ensuring that there is no diffusion of the doping element into the interface.
  • Transmission electron microscopy images were performed using a 200 KV FEG (Field Emission Gun).
  • the photoluminescence (PL) measurements were carried out using a USB2000 Ocean Optics spectrograph and a 1 mW nm laser diode.
  • the samples were passivated in hydrogen by annealing at 500 °C for 60 min in an atmosphere of 5% H 2 + 95% N 2 .
  • Measurements of the PL were taken at room temperature using an argon laser (Ar + ) at 405 nm, with a nominal power of 15mW.
  • the range of detection of the spectrograph covers wavelengths from 530 to 1100 nm.
  • I-V characteristics for illuminated cells were measured by an AM1.5G terrestrial photovoltaic lamp.
  • the spectrum of AM1.5G photovoltaic simulator lamp is considered to be similar to the Belgian sunlight.
  • I-V measurements under illumination were performed with a Keithley 2400 source-meter which allows sourcing and measuring voltage from ⁇ 5 ⁇ V (sourcing) and ⁇ 1 ⁇ V (measuring) to ⁇ 200V DC and current from ⁇ 10pA to ⁇ 1A.
  • the measurements were performed in a dark room which was shielded from most of external electromagnetic waves.
  • Figure 2 (a) shows RBS spectra recorded on the 240 nm SiO 2 /Si sample implanted with 70 keV Si ions with fluence of 2 ⁇ 10 17 Si/cm -2 .
  • a Gaussian-shape peak arises from ions backscattered from surface of the SiO 2 and the falls in the SiO 2 /Si interface reveals exactly the Gaussian distribution of the 70 keV Si ions into the 240 nm silicon oxide layer.
  • the range of the implanted ions is about 100 nm with typically FWHM of 100 nm.
  • Theoretical calculations have expected a sputtering of about 40 nm, resulting in the oxide layer being completely covered by the implanted ions.
  • Figure 2 (b) shows depth profiles extracted from the RBS spectra.
  • the depth profile of the implanted sample (as-implanted) shows a maximal excess concentration of 28 at.%.
  • a comparison of results obtained from annealed samples reveals that the Si depth distribution is not significantly modified for annealing times less than 30 minutes, but the contribution from the matrix is increased (12 to 28 %). This indicates that small Si-nc are progressively formed.
  • Fig. 2 (b) shows that for 60 minutes annealing, the depth distribution narrows, whilst the maximum concentration increases as the Si ions diffuse to the interface.
  • All implanted, heated and passivated samples exhibit photoluminescence emission with PL peaks at ⁇ 800 nm and 890 nm.
  • the 800 nm peak is observed for samples implanted with fluences of 6 x 10 16 Si/cm 2 and 1 x 10 17 Si/cm 2 ( Fig. 3 (a) and (b) ).
  • Figure 5 shows TEM images of Si-nc between 2 and 4 nm with cases of few coalescences probably arising from high Si concentration (28 %) and/or drastic annealing conditions.
  • the increase in concentration observing above in depth profiles exctracted from RBS measurements ( Figure 2 (b) ) could explain this behaviour.
  • Table 1 shows the photovoltaic properties of the illuminated Si QDs p-n devices made from non-implanted, implanted with two different doses (lines); and non-annealed, annealed, annealed and doped samples. Only PV cells fabricated by implantation annealing and doping (for n-p junction) yield a high electrical responses.
  • V oc 0,003 mV
  • Isc the thickness of the silicon oxide
  • Table 2 shows the photovoltaic properties of the illuminated Si QDs n-p devices made from samples implanted with a Si multiple energy implantations of 20, 35, 80 keV to fluences of 2.1 x 10 16 , 4.2 x 10 16 and 1.4 x 10 17 Si+/cm2.
  • Table 2 Comparison of I-V parameters for two different cells: a cell with 17 aluminum fingers (first line) and a cell with 5 aluminum. All samples used for cells fabrication have been annealed, doped with phosphorous and illuminated under AM1.5G. Here the value of V oc (mV) is 15 higher than in the case of single implantation device (see table 1).

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biophysics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Manufacturing & Machinery (AREA)
EP10175311A 2010-09-03 2010-09-03 Procédé de production de cellules photovoltaïques Withdrawn EP2426724A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP10175311A EP2426724A1 (fr) 2010-09-03 2010-09-03 Procédé de production de cellules photovoltaïques
CN2011800426403A CN103081131A (zh) 2010-09-03 2011-09-05 用于生产光伏电池的方法
US13/820,232 US20130273684A1 (en) 2010-09-03 2011-09-05 Process for the production of photovoltaic cells
EP11752224.3A EP2612368A1 (fr) 2010-09-03 2011-09-05 Procédé de production de cellules photovoltaïques
PH1/2013/500338A PH12013500338A1 (en) 2010-09-03 2011-09-05 Process for the production of photovoltaic cells
PCT/EP2011/065255 WO2012028738A1 (fr) 2010-09-03 2011-09-05 Procédé de production de cellules photovoltaïques
JP2013526498A JP2013536993A (ja) 2010-09-03 2011-09-05 太陽電池を生産するための方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP10175311A EP2426724A1 (fr) 2010-09-03 2010-09-03 Procédé de production de cellules photovoltaïques

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EP2426724A1 true EP2426724A1 (fr) 2012-03-07

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EP10175311A Withdrawn EP2426724A1 (fr) 2010-09-03 2010-09-03 Procédé de production de cellules photovoltaïques
EP11752224.3A Withdrawn EP2612368A1 (fr) 2010-09-03 2011-09-05 Procédé de production de cellules photovoltaïques

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US (1) US20130273684A1 (fr)
EP (2) EP2426724A1 (fr)
JP (1) JP2013536993A (fr)
CN (1) CN103081131A (fr)
PH (1) PH12013500338A1 (fr)
WO (1) WO2012028738A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104377114B (zh) * 2013-08-13 2017-04-05 国家纳米科学中心 一种锗量子点的生长方法、锗量子点复合材料及其应用
US11594459B2 (en) * 2021-02-11 2023-02-28 Taiwan Semiconductor Manufacturing Company, Ltd. Passivation layer for a semiconductor device and method for manufacturing the same

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WO2010110888A1 (fr) * 2009-03-23 2010-09-30 The Board Of Trustees Of The Leland Stanford Junior University Pile solaire de confinement quantique fabriquée par dépôt de couche atomique
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US20040261839A1 (en) 2003-06-26 2004-12-30 Gee James M Fabrication of back-contacted silicon solar cells using thermomigration to create conductive vias
US20070272995A1 (en) * 2006-05-23 2007-11-29 Ya-Chin King Photosensitive device
WO2009077103A1 (fr) 2007-12-14 2009-06-25 FRAUNHOFER-GESELLSCHAFT ZUR FÖRDERUNG DER FÖRDERUNG DER ANGEWANDTEN FORSCHUNG e.V. Photopile à couche mince et son procédé de fabrication

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DEMARCHE J ET AL: "Depth-profiling of implanted <28>Si by (alpha,alpha) and (alpha,p0) reactions", NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH, SECTION - B:BEAM INTERACTIONS WITH MATERIALS AND ATOMS, ELSEVIER, AMSTERDAM, NL, vol. 268, no. 11-12, 1 June 2010 (2010-06-01), pages 2107 - 2110, XP027046409, ISSN: 0168-583X, [retrieved on 20100225] *
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Publication number Publication date
CN103081131A (zh) 2013-05-01
WO2012028738A1 (fr) 2012-03-08
PH12013500338A1 (en) 2013-03-25
EP2612368A1 (fr) 2013-07-10
JP2013536993A (ja) 2013-09-26
US20130273684A1 (en) 2013-10-17

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